CN101349649B - Fiber optic sensor and method for making - Google Patents
Fiber optic sensor and method for making Download PDFInfo
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- CN101349649B CN101349649B CN2008101005134A CN200810100513A CN101349649B CN 101349649 B CN101349649 B CN 101349649B CN 2008101005134 A CN2008101005134 A CN 2008101005134A CN 200810100513 A CN200810100513 A CN 200810100513A CN 101349649 B CN101349649 B CN 101349649B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/104—Coating to obtain optical fibres
- C03C25/106—Single coatings
- C03C25/1061—Inorganic coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/12—General methods of coating; Devices therefor
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02057—Optical fibres with cladding with or without a coating comprising gratings
- G02B6/02076—Refractive index modulation gratings, e.g. Bragg gratings
- G02B6/0208—Refractive index modulation gratings, e.g. Bragg gratings characterised by their structure, wavelength response
- G02B6/021—Refractive index modulation gratings, e.g. Bragg gratings characterised by their structure, wavelength response characterised by the core or cladding or coating, e.g. materials, radial refractive index profiles, cladding shape
- G02B6/02104—Refractive index modulation gratings, e.g. Bragg gratings characterised by their structure, wavelength response characterised by the core or cladding or coating, e.g. materials, radial refractive index profiles, cladding shape characterised by the coating external to the cladding, e.g. coating influences grating properties
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
- G01N2021/7706—Reagent provision
- G01N2021/7726—Porous glass
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Abstract
A fiber optic sensor including a fiber 10 having a modified surface integral with the fiber wherein the modified surface includes an open pore network with optical agents 40 dispersed within the open pores 30 of the open pore network. Methods for preparing the fiber optic sensor are also provided. The fiber optic sensors can withstand high temperatures and harsh environments.
Description
Statement about the government-funded research and development
The present invention utilizes government-funded to finish, and the contract number that USDOE gives is DE-FC26-05NT42438.Government enjoys some right in the present invention.
Invention field
The present invention relates to a kind of method for preparing fiber optic sensor (fiber optic sensor), relate more specifically to the fiber optic sensor for rugged surroundings.
Background of invention
Fiber optic sensor can be used for monitoring dynamic, the chemistry relevant with environmental change and physical process.General fiber optic sensor makes sensor material and material or environmental interaction monitored, that detect and/or survey under the help of the supporter of one or more types.Fiber optic sensor comprises based on the chemical environment of uniqueness determines the optical agents that optical index changes.In order correctly to play a role, optical agents must be arranged in the optical clear supporting body structure, and this supporting body structure holds optical agents and allows optical agents and environment or matter interaction monitored, that detect or survey.
Traditional fiber optic sensor often is restricted under the relatively gentle temperature conditions, and when in high temperature and/or rugged surroundings, for example combustion gas or steam turbine exhaust device when using under the boiler of coal heating and the aircraft engine, begin to damage.
The U.S. Patent No. 5,496,997 of authorizing Pope discloses a kind of optical fiber, and wherein the far-end of optical fiber connects the amorphous silica microballoon by adhesive material.Because adhesive phase can damage under high temperature or rugged surroundings, this sensor can break down under rugged surroundings.
Need a kind of fiber optic sensor that can stand high temperature and rugged surroundings.
Summary of the invention
In one embodiment, fiber optic sensor comprises optical fiber (fiber), and this optical fiber has the modified surface that becomes integral body with optical fiber, and described modified surface comprises the perforate network and is arranged on the interior optical agents of perforate of perforate network.
In another embodiment, a kind of method for preparing fiber optic sensor comprises stupalith is applied on the optical fiber, and forms the perforate network structure, optical agents is dispersed in the hole of perforate network, makes stupalith and optical fiber form integral body.
In another embodiment, a kind of method for preparing fiber optic sensor comprises that the stupalith potpourri that will comprise stupalith and optical agents is applied on the optical fiber, forms the perforate network structure in stupalith, makes stupalith and optical fiber form integral body.
Various embodiments provide the fiber optic sensor that can stand high temperature and rugged surroundings.
Brief description of the drawings
Figure 1A is the figure of the modified surface of the optical fiber before the demonstration thermal treatment.
Figure 1B is the figure of the modified surface of optical fiber after the description thermal treatment.
Fig. 2 A is the figure that describes the modified surface of the front optical fiber of thermal treatment.
Fig. 2 B is the figure of the modified surface of optical fiber after the description thermal treatment.
Fig. 3 is presented at 25 ℃ of (room temperature) N
2Be separated out existing 5%H in the middle of the gas
2H
2The table of response light reflectivity curve.This table with watt/time (minute) export as signal.
Fig. 4 is presented at 120 ℃ of N
2Be separated out existing 5%H in the middle of the gas
2H
2The table of response light reflectivity curve.This table with a watt vs time (minute) export as signal.
Fig. 5 is presented at 172 ℃ of N
2Be separated out existing 5%H in the middle of the gas
2H
2The table of response light reflectivity curve.This table with a watt vs time (minute) export as signal.
Fig. 6 is presented at 355 ℃ of N
2Be separated out existing 5%H in the middle of the gas
2H
2The table of response light reflectivity curve.This table with a watt vs time (minute) export as signal.
Fig. 7 is presented at 425 ℃ of N
2Be separated out existing 5%H in the middle of the gas
2H
2The table of response light reflectivity curve.This table with a watt vs time (minute) export as signal.
Fig. 8 is presented at 525 ℃ of N
2Be separated out existing 5%H in the middle of the gas
2H
2The table of response light reflectivity curve.This table with a watt vs time (minute) export as signal.
Fig. 9 sums up H
2The table of the relative response of gas.This table be relative response (δ vsV) vs temperature (℃).
Figure 10 shows the response time (minute) vs temperature (℃).
Figure 11 is presented at 425 ℃ of N
2Be separated out the table of the CO response light reflectivity curve of existing 5%CO in the middle of the gas.This table with a watt v s time (minute) export as signal.
Figure 12 is presented at 525 ℃ of N
2Be separated out the table of the CO response light reflectivity curve of existing 5%CO in the middle of the gas.This table with a watt vs time (minute) export as signal.
Figure 13 is presented at 280 ℃ of N
2Be separated out the table of the CO response light reflectivity curve of existing 5%CO in the middle of the gas.This table with a watt vs time (minute) export as signal.
Figure 14 is presented at 525 ℃ of N
2Be separated out the table of the CO response light reflectivity curve of existing 5%CO in the middle of the gas.This table with a watt vs time (minute) export as signal.
The concise and to the point description of invention
Singulative " one " " is somebody's turn to do " and comprises plural number, unless context conclusivelys show in addition.The end points of all scopes of narration same characteristic features is end points independent combination and that comprise narration.All lists of references are combined for reference.
The modifier that is connected with quantity " approximately " comprises the value of statement, and has the implication (for example, comprising the deviation range relevant with specific quantity mensuration) that context shows.
Event or the situation of description may occur or may not occur thereafter " to choose " expression wantonly, the material of perhaps determining thereafter may exist or may not exist, this description comprises the situation that time or situation occur or material exists, and event or situation does not occur or the non-existent situation of material.
In one embodiment, fiber optic sensor comprises optical fiber, and this optical fiber has the modified surface that becomes integral body with optical fiber, and described modified surface comprises the perforate network and is arranged on the interior optical agents of perforate of perforate network.
Fiber optic sensor can be used for monitoring physics, electricity and chemical parameters.In one embodiment, this fiber optic sensor is the man-made fiber optical sensor.
Optical fiber comprises fiber cores and optional, fibre cladding.Fibre cladding if exist, at least part ofly forms waveguide around fiber cores, described waveguide along the axle longitudinal extension and comprise have refractive index (or optical thickness) thus the part that changes forms the optical diffraction grating.
Fiber cores is transparent, can comprise sapphire, porous sol-gel derived bioglass or fused silica material.
Fibre cladding can be transparent, can be made by the material identical with fibre core, but have low-refraction.In one embodiment, fibre cladding comprises glass or silicon dioxide.
At least part of optical fiber surface is modified.Modified surface can be positioned at fiber cores or the fibre cladding of optical fiber, if present.The modification of optical fiber comprised by any conventional method stupalith is applied on the surface of optical fiber.When stupalith solidifies, it forms porous and optically transparent supporting body structure, and this structure is three-dimensional matrice or the grid type structure with a plurality of interconnective holes, and described hole extends through whole supporting body structure and forms the perforate network.
The size in described hole can be to allow to detect any suitable size that gas passes supporting body structure.In one embodiment, its diameter of the size in described hole is at most about 150nm.In another embodiment, its diameter of the size in described hole is from about 1nm to about 150nm.In conventional method when material cured by regulating in a usual manner the size that time and temperature can control punchs.
In one embodiment, apply (immersing coating) or apply the surface that film is applied to stupalith optical fiber by spraying, brushing, roller coating, perfusion (pouring), dipping (dipping), submergence.In a kind of mode, by the surface modification of coating surface with optical fiber.In another embodiment, by the modification of impregnated optical fiber effects on surface.In another embodiment, carry out modification by forming from the teeth outwards the film effects on surface.
Described stupalith can be silicon dioxide, aluminium oxide or titanium dioxide.Aluminium oxide, titanium dioxide and silicon dioxide can be derived from organic-metallics, for example orthosilicic acid tetraethoxy ester.In one embodiment, described stupalith comprises silicon dioxide.
Optical agents is the sensor of the specific chemical environment of chemical detection and detection fiber covering optical index.Optical agents can be the sensor of any type known in the art.In one embodiment, optical agents can be metal or transition metal.In one embodiment, transition metal is to contain the 8-10 of family transition metal, ruthenium for example, rhodium, any compound of platinum and palladium.In one embodiment, optical agents is palladium.In another embodiment, optical agents can comprise metal oxide.In another embodiment, metal oxide can comprise tin ash, yttria (yittrium oxide), vanadium oxide, titanium dioxide and tungsten oxide.
Optical agents is arranged in perforate and at least part of surrounding air that is exposed to of perforate network.Optical agents utilizes any conventional method to be arranged in the perforate by optical agents being scattered in the perforate network two.Optical agents can or apply modified surface with optical agents by spraying, brushing, roller coating, perfusion, dipping, immersion and be dispersed.In one embodiment, by modification optical fiber is dipped into the solution that contains optical agents, optical agents is dispersed in the perforate of perforate network.Optical agents and water or alcohol can be mixed with described solution.Combine closely by stupalith and optical fiber surface, stupalith and optical fiber form integral body and do not need adhesive material or adhesive phase.Thereby stupalith infiltrates the surface of optical fiber on the surface of optical fiber formation integral body and modification, and it effectively replaces optical fiber surface with new modified surface.Can make stupalith and optical fiber form integral body by any method that is suitable for making the stupalith sclerosis and being closely adhered to optical fiber surface.The stupalith that hardens forms the perforate network of compact structure, environment or material that it holds on the spot optical agents and contact is detected, monitor or survey.Described perforate network holds in heat, chemistry and the solid and stable supporting body structure of machinery and protects optical agents.
In one embodiment, stupalith can and be attached on the fiber by thermal treatment, drying or radiation hardening.In another embodiment, stupalith is through bakingout process.Thermal treatment can be undertaken by any conventional method.In one embodiment, modified fibre is heated to many about 4 hours between about 300 ℃ and about 600 ℃.In one embodiment, modified fibre heated about 1 to about 3 hours.Higher temperature or long period laser heating finally can cause the perforate network to become fully closely, have on a small quantity or do not have hole.
In another embodiment, a kind of method for preparing fiber optic sensor comprises stupalith is applied on the optical fiber to form the perforate network structure, optical agents is dispersed in the hole of perforate network, makes stupalith and optical fiber form integral body.
As mentioned above, stupalith can be silicon dioxide, aluminium oxide or titanium dioxide.Aluminium oxide, titanium dioxide and silicon dioxide can be derived from organic metal, for example orthosilicic acid tetraethoxy ester.
In one embodiment, stupalith comprises that diameter is at the spheric grain of about 20nm to the 700nm scope.By the scanning electron microscopy measurement diameter.In one embodiment, spheric grain is single size.In another embodiment, at least about 95% spheric grain the mean diameter of spheric grain about 10% in.
In another embodiment, stupalith comprises the spheric grain of silicon dioxide.The spheric grain of silicon dioxide can add and contain alcohol by with silica precursor orthosilicic acid tetraethoxy ester for example, and the solution of the ammoniacal liquor of optional 1-50% (weight) and making.The size of particle is by the relative concentration control of water, ammonia and alcohol.In one embodiment, described alcohol is ethanol.The quantity of alcohol is in about 10-70% of solution weight (weight) scope.The quantity of ammonia is in about 1-50% of solution weight (weight) scope.The quantity of water is about 10-70% (weight) of solution weight.The quantity of silica precursor is about 1-10% (weight) of solution weight.
In one embodiment, the stupalith that comprises spheric grain applies or applies film and be applied on the optical fiber surface by spraying, brushing, rolling, perfusion, dipping, submergence.In one embodiment, by in the aqueous solution that optical fiber is impregnated into the ceramic spherical particle optical fiber surface being carried out modification.Spheric grain is adhered to optical fiber surface by Van der Waals force.When the water of solution becomes dry, drag the tight network that spheric grain enters the open space that forms contact particle and perforate from the capillary force that evaporates moisture film.
Optical agents is scattered in the perforate of perforate network by any conventional method.As previously mentioned, optical agents can or apply modified surface with optical agents by spraying, brushing, roller coating, perfusion, dipping, immersion and is dispersed.In one embodiment, optical agents by Solution Dispersion in the perforate network.Optical agents is added in the solution that contains water or alcohol, and the optical fiber with modified surface immerses this solution.Repeating that optical agents is distributed to the step of perforate network can be for increasing the concentration of optical agents on optical fiber.Optical agents is arranged in the perforate of perforate network, and at least part of environment or material that will be detected that be exposed to.
By any be suitable for making stupalith sclerosis and with the method that optical fiber is combined closely, make stupalith and optical fiber form integral body and not need adhesive material or adhesive phase.
Figure 1A is the figure that describes the front optical fiber 10 of thermal treatment.Modification is carried out by applying the stupalith 20 that comprises the ceramic spherical particle in the surface of optical fiber 10.Ceramic particle 20 is adhered on the surface of optical fiber 10 and forms the perforate network of contact particle and open space 30.Optical agents 40 is dispersed in the perforate 30 of perforate network.Figure 1B is the figure of the optical fiber 10 after the description thermal treatment.When thermal treatment, thereby ceramic spherical particle 20 hardens and form the whole perforate network that forms tight stupalith 20 with optical fiber 10.Optical agents 40 is supported and remain on original position by the perforate network of stupalith 20, and is exposed to and wants measured environment or material.
In another embodiment, a kind of method for preparing fiber optic sensor comprises that the stupalith potpourri that will comprise stupalith and optical agents is applied on the optical fiber, forms the perforate network structure of stupalith, makes stupalith and optical fiber form integral body.
The stupalith potpourri comprises stupalith and optical agents.Prepare the stupalith potpourri by optical agents being added stupalith.Can utilize any conventional method that optical agents is mixed with stupalith.In one embodiment, optical agents and stupalith mix in solution.In another embodiment, the solution of preparation orthosilicic acid tetraethoxy ester, pure and mild optical agents.
Utilize any conventional method that the stupalith potpourri is applied on the optical fiber surface.In one embodiment, apply or apply film stupalith is applied on the surface by spraying, brushing, roller coating, perfusion, dipping, submergence.In one embodiment, the surface by coated fiber applies the stupalith potpourri.In another embodiment, apply the stupalith potpourri by impregnated optical fiber.In another embodiment, the film that comprises the stupalith potpourri is formed on the surface of optical fiber.
Can for example drying or thermal treatment form the perforate network by any method that is suitable for the hardened ceramic material.When stupalith drying or heating, stupalith begins gel, begins to form the crack at stupalith.The crack is closely providing the perforate network in the stupalith.The speed that changes by controlled humidity and the quantity that can control the crack by heating and rate of drying.
By any be suitable for making stupalith sclerosis and with the method that optical fiber is combined closely, make stupalith and optical fiber form integral body and not need adhesive material or adhesive phase.
In another embodiment, the stupalith potpourri also comprises polymkeric substance.Described polymkeric substance can be the organic polymer of any type, and it for example can decompose in heat treatment step at elevated temperatures.In one embodiment, described organic polymer can be polyolefinic oxide, emulsion polymer, polyester and polypropylene.In another embodiment, described organic polymer comprises polyethylene oxide or polypropyleneoxide.Described polymkeric substance adds in the stupalith with about 0.1 amount to about 10% (volume) of stupalith.
Polymkeric substance helps closely producing the perforate network in the stupalith by produce crack and space in ceramic coat, stupalith is heat-treated by any conventional method, polymkeric substance decomposes in heat treatment step and form the space in coating, and this can increase the perforate in the compact ceramic.Structural failure but enough littlely can not caused to ceramic layer by void diffusion in space in the ceramic coat and the crack enough large gas that allows.In one embodiment, the diameter in space can arrive about 100 μ (μ m) for about 10 μ.
Fig. 2 A is for showing the figure of the optical fiber 200 that thermal treatment is front.The potpourri of stupalith 210, optical agents 220 and polymkeric substance 230 is applied to the surface of optical fiber 200, and allows under controlled humidity dry to cause the crack (not shown) in the tight stupalith.Fig. 2 B is the figure of the optical fiber 200 after the demonstration thermal treatment.Modified surface is through bakingout process, and when thermal treatment, stupalith 210 hardens and combines closely with optical fiber 200.Polymkeric substance 230 decomposes, and stays space 240 in stupalith 210.Optical agents 220 is supported and remains on by original position in the perforate network of stupalith 210 interior formation, and is exposed in the environment or material that will detect.
For those skilled in the art can realize the present invention better, by way of example and unrestrictedly provide following embodiment.
Embodiment
Example 1
The orthosilicic acid tetraethoxy ester of preparation 89.5% (weight), the palladium of 10.5% (weight), and based on the potpourri of the 1-propyl alcohol of 40% (weight) of orthosilicic acid tetraethoxy ester and palladium weight.Form silicon dioxide by orthosilicic acid tetraethoxy ester and 1-propyl alcohol, the mean diameter of its spheric grain is 300nm, wherein the diameter of 95% particle mean diameter 10% in.
The film of the potpourri of silicon dioxide and palladium is applied on the substrate of glass, 400 ℃ of thermal treatments 2 hours.Film thickness is about 100 μ m.
The hydrogen of detection fibers optical sensor response between room temperature and 525 ℃.Fig. 3-8 shows respectively 25 ℃ (room temperatures), 120 ℃, and 172 ℃, 355 ℃, 425 ℃ and 525 ℃ of lower N
2Be separated out existing 5%H in the middle of the gas
2H
2The response light reflectivity curve.Detect H at about 355 ℃ of sensors at the most
2Sensitive.
Sum up H at Fig. 9
2The relative response of gas.Relative response is the merchant of signal change and signal level.Its value utilizes the fastest change signal to estimate by average.The result is presented in the temperature range that film can detect, and increases along with temperature increases sensitivity.
Figure 10 is response time and temperature.The response time value utilizes the fastest change signal to estimate by average.The result is presented in the temperature range that film can detect, and temperature is higher, and the response time is shorter, and this increases corresponding with temperature rising chemical reaction velocity.
Prior art at room temperature interacts with hydrogen based on the sensitive material of palldium alloy, allows to utilize light and optical fiber technology to survey and detection hydrogen, does not survey but be presented under the higher temperature.Ref.X B é venot, A Trouillet, C Veillas, H Gagnaire, and M.Cl é ment, Meas.Sci.Technol.13,118-124 (2002).
Example 2
The orthosilicic acid tetraethoxy ester of preparation 80% (weight), the tin ash of 15% (weight), the palladium of 5% (weight), and based on the potpourri of the 1-propyl alcohol of 8% (weight) of orthosilicic acid tetraethoxy ester, palladium and tin ash weight.Prepare silicon dioxide by orthosilicic acid tetraethoxy ester and 1-propyl alcohol, silicon dioxide is that mean diameter is the spheric grain of 300nm, and wherein, the diameter of 95% particle is in 10% mean diameter.
The film of the potpourri of silicon dioxide, tin ash and palladium was applied on the substrate of glass, 400 ℃ of heat treated 2 hours.Film thickness is about 20 μ m.
The detection fibers optical sensor is to the response of carbon monoxide between 325 ℃ and 525 ℃.Figure 11 and 12 is respectively at 425 ℃ and 525 ℃ of lower N
2Be separated out the CO response light reflectivity curve of existing 5%CO in the middle of the gas.This sensor Sensitive Detection CO in temperature range.
At 525 ℃ of other detections 1%, 2% and 3%CO.The result shows at 525 ℃ CO gas to be had remarkable response.Change for different CO concentration signal levels.
Example 3
The orthosilicic acid tetraethoxy ester of preparation 89.5% (weight), the palladium of 10.5% (weight), and based on the potpourri of the 1-propyl alcohol of 20% (weight) of orthosilicic acid tetraethoxy ester, palladium weight.Prepare silicon dioxide by orthosilicic acid tetraethoxy ester and 1-propyl alcohol, silicon dioxide is that mean diameter is the spheric grain of 300nm, and wherein, the diameter of 95% particle is in 10% mean diameter.
The film of the potpourri of silicon dioxide and palladium is applied on the substrate of glass, 500 ℃ of thermal treatments 2 hours.Film thickness is about 100 μ m.
From the response of room temperature to 525 ℃ detection fibers optical sensor to carbon monoxide.At room temperature the detection of CO do not had signal, but at high temperature have good signal output.Figure 13 and 14 is respectively at 280 ℃ and 525 ℃ of lower N
2Be separated out the CO response light reflectivity curve of existing 5%CO in the middle of the gas.As shown in figure 14, also powerful rapidly to the response of CO gas.
Although for the purpose of giving an example has been illustrated typical embodiment, the description of front should not be considered to the restriction to protection domain.Therefore, those skilled in the art can carry out various improvement, modification and substitute, and do not depart from its spirit and scope.
Claims (28)
1. fiber optic sensor, comprise optical fiber, the modified surface that this optical fiber has covering and becomes integral body with optical fiber, described modified surface is made by stupalith is applied on the optical fiber, and comprise the perforate network and be dispersed in optical agents in the perforate of perforate network, wherein said modified surface and described optical fiber surface are combined closely, described optical agents comprises the 8-10 group 4 transition metal or is selected from the metal oxide of tin ash, yttria, vanadium oxide, titanium dioxide and tungsten oxide, and described modified surface is on described covering.
2. the sensor of claim 1, wherein stupalith comprises silicon dioxide.
3. the sensor of claim 1, wherein optical agents is the transition metal that is selected from ruthenium, rhodium, platinum and palladium.
4. the sensor of claim 3, wherein transition metal is palladium.
5. a method for preparing fiber optic sensor comprises
Stupalith is applied on the optical fiber with covering, and forms the perforate network structure, thereby obtain the fiber of modification,
Optical agents is dispersed in the hole of perforate network,
And make stupalith and optical fiber form integral body,
Wherein
The described step that applies stupalith forms by applying stupalith to described covering,
And described optical agents comprises the 8-10 group 4 transition metal or is selected from the metal oxide of tin ash, yttria, vanadium oxide, titanium dioxide and tungsten oxide.
6. the method for claim 5 wherein applies stupalith by applying described fibre cladding.
7. the method for claim 5 wherein is applied to stupalith on the fibre cladding surface by forming film.
8. the method for claim 5 is wherein passed through with the stupalith coating surface the fibre cladding modifying surface.
9. the method for claim 5, wherein the solution by surface impregnation being entered to comprise stupalith is to the fibre cladding modifying surface.
10. the method for claim 5, wherein stupalith comprises spheric grain.
11. the method for claim 5, wherein said stupalith comprises silicon dioxide.
12. method according to claim 10, wherein
The thermal treatment stupalith, with formation perforate network, and
The fiber impregnation of described modification is entered to comprise in the solution of optical agents, thereby optical agents is distributed in the hole of perforate network.
13. the method for claim 5, wherein said optical agents are transition metal or metal oxide.
14. the method for claim 13, wherein said transition metal are palladium.
15. the method for claim 5, wherein said fiber was at 300 ℃ of-600 ℃ of lower thermal treatment 1-4 hours.
16. method for preparing fiber optic sensor, comprise that the stupalith potpourri that will comprise stupalith and optical agents is applied on the optical fiber with covering, in stupalith, form the perforate network structure, and make stupalith and optical fiber form integral body, the wherein said step that applies the stupalith potpourri is by applying the stupalith compositions of mixtures to described covering, and described optical agents comprises the 8-10 group 4 transition metal or is selected from the metal oxide of tin ash, yttria, vanadium oxide, titanium dioxide and tungsten oxide.
17. the method for claim 16 wherein applies described stupalith potpourri by applying described cladding of fiber.
18. the method for claim 16 wherein is applied to the stupalith potpourri on the fibre cladding surface by forming film.
19. the method for claim 16, wherein the solution by surface impregnation being entered to comprise the stupalith potpourri is to the fibre cladding modifying surface.
20. the method for claim 16, wherein said stupalith comprises spheric grain.
21. the method for claim 16, wherein said stupalith comprises silicon dioxide.
22. the method for claim 16, wherein said optical agents are transition metal or metal oxide.
23. the method for claim 22, wherein said transition metal are palladium.
24. the method for claim 16, wherein said fiber was at 300 ℃ of-600 ℃ of lower thermal treatment 1-4 hours.
25. the method for claim 16, wherein said stupalith potpourri also comprises polymkeric substance.
26. the method for claim 25, wherein said polymkeric substance is organic polymer.
27. pass through the sensor of the method preparation of claim 14.
28. pass through the sensor of the method preparation of claim 23.
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US8019190B2 (en) * | 2009-03-30 | 2011-09-13 | General Electric Company | Optical sensors, systems, and methods of making |
US8135247B2 (en) * | 2009-03-30 | 2012-03-13 | General Electric Company | Packaged sensors and harsh environment systems with packaged sensors |
US9419167B2 (en) * | 2010-12-01 | 2016-08-16 | 1366 Technologies, Inc. | Making semiconductor bodies from molten material using a free-standing interposer sheet |
WO2017132480A1 (en) * | 2016-01-29 | 2017-08-03 | Corning Incorporated | Optical fiber apparatus with high divergence angle and light source system using same |
JP6915859B2 (en) * | 2017-08-08 | 2021-08-04 | 学校法人 創価大学 | Optical fiber hydrogen sensor and its manufacturing method |
CN108645827B (en) * | 2018-05-11 | 2021-06-22 | 武汉理工大学 | Ultra-sensitive NO sensor based on simplified microstructure optical fiber |
GB2615737A (en) * | 2021-12-23 | 2023-08-23 | Oxsensis Ltd | Optical sensor |
JP7081864B1 (en) * | 2021-12-24 | 2022-06-07 | 株式会社ヒキフネ | Manufacturing method of coated fiber, sensor device, monitoring device and coated fiber |
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US7720321B2 (en) | 2010-05-18 |
EP2017659A1 (en) | 2009-01-21 |
CN101349649A (en) | 2009-01-21 |
JP5025561B2 (en) | 2012-09-12 |
EP2017659B1 (en) | 2016-03-30 |
US20090022449A1 (en) | 2009-01-22 |
JP2009025289A (en) | 2009-02-05 |
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